EP0709831A2 - Dispersants - Google Patents
Dispersants Download PDFInfo
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- EP0709831A2 EP0709831A2 EP95119618A EP95119618A EP0709831A2 EP 0709831 A2 EP0709831 A2 EP 0709831A2 EP 95119618 A EP95119618 A EP 95119618A EP 95119618 A EP95119618 A EP 95119618A EP 0709831 A2 EP0709831 A2 EP 0709831A2
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- methyl ethyl
- ethyl ketone
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Classifications
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
- G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
- G11B5/702—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the bonding agent
- G11B5/7026—Radiation curable polymers
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
- G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
- G11B5/7013—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the dispersing agent
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
- G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
- G11B5/702—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the bonding agent
- G11B5/7021—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the bonding agent containing a polyurethane or a polyisocyanate
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
- G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
- G11B5/702—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the bonding agent
- G11B5/7023—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the bonding agent containing polyesters, polyethers, silicones, polyvinyl resins, polyacrylresins or epoxy resins
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/73—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer
- G11B5/735—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer characterised by the back layer
Definitions
- the present invention relates to novel, monomeric, oligomeric or polymeric dispersants comprising at least one dispersing moiety and at least one specified radiation curable moiety.
- the present invention provides a novel ⁇ -methylstyrene functionalized dispersant, wherein said dispersant comprises at least one dispersing moiety and at least one radiation crosslinkable moiety of the formula: wherein said formula represents:
- Dispersants of the present invention may be prepared from an ⁇ -methylstyrene functionalized, isocyanate of the formula wherein this formula represents hereinafter referred to as "meta TMI", or hereinafter referred to as "para TMI”.
- the ⁇ -methylstyrene functionalized isocyanate is meta TMI.
- TMI has been described in Dexter et al., "M-TMI, A Novel Unsaturated Aliphatic Isocyanate", Journal of Coatings Technology, Vol. 58, No. 737, pp. 43-47 (June 1986); U.S. Pat. No. 4,853,478; U.S. Pat. No. 4,839,230; U.S. PAT. No. 4,788,303; and U.S. Pat. No. 4,617,349.
- the subject invention provides a novel class of dispersants comprising monomeric, oligomeric, or polymeric dispersants comprising at least one dispersing moiety and at least one radiation curable moiety of the formula wherein this formula represents Such dispersants shall be referred to hereinafter as " ⁇ -methylstyrene functionalized" dispersants.
- suitable dispersing moieties include -SO3M, wherein M is Na+, K+, Li+, NH4+, and the like; quaternary ammonium moieties; and the like.
- novel ⁇ -methylstyrene functionalized dispersants are capable of crosslinking with the other radiation curable binder materials of the type described in the parent application to this divisional application, when exposed to ionizing radiation in the presence of the free radical generator.
- One preferred ⁇ -methylstyrene functionalized dispersant may be prepared by reacting TMI with a phosphorylated polyoxyalkyl polyol, exemplified by the following formula: such that the NCO groups of the TMI react with the hydroxy groups of the polyol.
- m is an integer from 1 to 5.
- Phosphorylated polyoxyalkyl polyols are described in U.S. Pat. No. 4,889,895. All or only a portion of the hydroxy groups of the phosphorylated polyoxyalkyl polyol may be reacted with NCO groups of the TMI. Preferably, the TMI is reacted with the polyol in an amount such that the ratio of NCO groups to OH groups is about 0.6.
- Another preferred difunctional dispersant may be prepared by reacting TMI with a polyoxyalkylated quaternary ammonium polyol such as the Emcol brand dispersing agents commercially available from Witco Chemical, New York, New York.
- the Emcol materials are exemplified by the formula In the above formula, ⁇ X typically is phosphate, acetate, or chloride. All or only a portion of the hydroxy groups of such polyols may be reacted with the NCO groups of the TMI. It is noted that the Emcol materials typically contain other free polyols.
- the TMI is reacted with such polyols in an amount such that the ratio of NCO groups to OH groups of the polyoxyalkylated quaternary ammonium polyol is about 2.2:1. In this way, all of the hydroxy groups of the other polyols and the polyoxyalkylated quaternary ammonium polyol are reacted with TMI.
- the dispersants of the subject invention can be used in the field of magnetic recording media.
- Magnetic recording media generally comprise a magnetizable layer coated on at least one side of a nonmagnetizable substrate.
- the magnetizable layer comprises a magnetic pigment dispersed in a polymeric binder.
- the magnetizable layer may also include other components such as lubricants; abrasives; thermal stabilizers; antioxidants; wetting agents,; antistatic agents; fungicides; bacteriocides; surfactants; coating aids; nonmagnetic pigments; and the like.
- Some forms of magnetic recording media such as flexible magnetic recording tape, also have a backside coating applied to the other side of the nonmagnetizable substrate in order to improve the durability,conductivity, and tracking characteristics of the media.
- the backside coating typically comprises a polymeric binder, but may also include other components such as dispersants; lubricants; abrasives; thermal stabilisers; antioxidants; wetting agents; antistatic agents; fungicides; bacteriocides; surfactants; coating aids; nonmagnetic pigments; and the like.
- the components of the magnetizable layer preferably include at least one dispersant to facilitate the dispersion of the magnetic pigment in the polymeric binder.
- a preferred class of dispersants comprises novel monomeric, oligomeric, or polymeric dispersants of the present invention.
- Radiation curable polymer samples of the present invention were prepared under ambient conditions by reacting a hydroxy functional polymer (PKHH UCAR phenoxy resin commercially available from Union Carbide Corporation) with meta-TMI in the following amounts: Sample Parts by weight of Hydroxy Functional Polymer Parts by weight of meta-TMI % OH groups reacted with meta-TMI 1 100.0 14.16 20 2 100.0 35.40 50 3 100.0 42.46 60 4 100.0 56.62 80
- the hydroxy-functional polymer was first dissolved in 233 parts by weight methyl ethyl ketone. Next, 200 ppm (based on total weight of the hydroxy functional polymer and the meta-TMI) of BHT gellation inhibitor and 0.15 weight percent (based on the total weight of the hydroxy functional polymer and the meta-TMI) of dibutyltindilaurate catalyst were added to the solution with mixing. The meta-TMI was then slowly added with mixing. After all of the meta-TMI had been added, the reaction between the hydroxy-functional polymer and the meta-TMI was monitored by measuring the IR absorption peak of the NCO group (2250 cm ⁇ 1) from the meta-TMI. The reaction was deemed to be complete when an IR absorption peak for the NCO group could no longer be detected.
- reaction mixture was cooled to room temperature.
- additional methyl ethyl ketone may be added to the reaction mixture in order to reduce the weight percent solids to about 33% solids. Adding additional solvent in this manner lowers the viscosity of the reaction mixture, thereby facilitating subsequent processing.
- the Tg of Samples 1, 2, 3, and 4 were 80°C, 72°C, 68°C and 65°C, respectively, as measured using the DSC technique.
- a magnetic dispersion of the present invention was prepared from the following ingredients: Ingredient Parts by Weight ⁇ -Fe2O3 100.00 Carbon black 5.00 Al2O3 7.00 Phosphate acid ester acrylate commercially available as L-51 from Lord Corporation (50% by weight in tetrahydrofuran) 10.00 Emcol Phosphate 2.00 Radiation curable polymer (Sample 3 from Example 1) (32% by weight in methyl ethyl ketone) 67.50 Methyl ethyl ketone 135.48 To prepare the dispersion, these ingredients were combined and then milled until smooth.
- the resulting magnetic recording medium was tested for crosslink density using the "MEK double rub” test. According to this test, the sample was rubbed vigorously with back and forth rubs using a paper towel that had been soaked in methyl ethyl ketone. Failure occurred when the rubbing action broke through the magnetic coating to the polyester film. The magnetic coating of this sample was not broken through to the polyester film until after 30 back and forth rubs.
- a magnetic recording medium was prepared using the procedure of RE 2 except that hydantoin hexacrylate was used in place of PETA.
- the resulting magnetic recording medium passed the MEK double rub test without showing any break through to the polyester film until after 10 back and forth rubs.
- a magnetic recording medium was prepared using the procedure of RE 2 except that tris(2-hydroxyethyl) triacrylate (available as Sartomer 368 from Sartomer Co.) was used in place of PETA.
- the resulting magnetic recording medium passed the MEK double rub test without showing any break through to the polyester film until after 20 back and forth rubs.
- a first step 100.00 parts by weight gamma-Fe2O3, 9.00 parts by weight of carbon black, 24.14 parts by weight of Disperbyk-160 (29% by weight solution of a polyurethane polymer having pendant tertiary amine wetting groups commercially available from BYK-Chemie USA), 18.09 parts by weight of a 33% by weight solution of a radiation curable polymer (prepared in accordance with Sample 4 from Example 1) in methyl ethyl ketone, 59.73 parts by weight of a 15% by weight solution of a polyurethane polymer (Estane 5703 commercially available from The B. F.
- pre-dispersed alumina means that 100 parts by weight of alumina had previously been dispersed in 40.1 parts by weight of methyl ethyl ketone, 18.2 parts by weight of a radiation curable polymer (prepared in accordance with Sample 2 from Example 1), 20.7 parts by weight of Disperbyk-160, 0.07 parts by weight of propyl gallate, and 0.07 parts by weight of Irgafos 168.
- the resulting blend was then gravure coated onto both sides of a 3-mil, pre-primed polyester substrate at a 228 x 10 ⁇ 6 cms (90 microinch) caliper.
- the coated substrate was then passed through a randomizer, dried in an oven at 71°C (160°F) calendered, and cured with 10 Mrads of electron beam radiation (200 keV) in an inert atmosphere comprising no more than 75 ppm O2.
- the resulting magnetic recording medium showed a 60° gloss of 120 and a squareness of 0.50.
- the resulting media would be particularly suitable for forming magnetic recording diskettes.
- pre-dispersed alumina means that 100 parts by weight of alumina had previously been dispersed in 1 part by weight Emcol Phosphate, 1.3 parts by weight of a 75% by weight solution of phosphorylated polyoxyalkyl polyol in toluene, 30.6 parts by weight methyl ethyl ketone, and 3.4 parts by weight of cyclohexanone.
- the following ingredients were added in order under high shear mixing: 0.33 parts by weight of myristic acid, 1.67 parts by weight of isocetyl stearate, 3.38 parts by weight of Ebecryl 220, and 69.2 parts by weight of methyl ethyl ketone.
- the resulting blend was then gravure coated onto both sides of a 76.2 ⁇ m (3 mil), pre-primed polyester substrate at a 114 x 10 -6 cms (45 microinch) caliper.
- the coated substrate was then passed through a randomizer, dried in an oven at 71°C (160°F) calendered, and cured with 10 Mrads of electron beam radiation (200 keV) in an inert atmosphere comprising no more than 75 ppm O2.
- the resulting magnetic recording medium showed a squareness of 0.7, a 60° gloss of 130, and a remanence, B R , of 800 gauss.
- the resulting magnetic recording medium would be particularly suitable for forming magnetic recording diskettes.
- the following ingredients were added in order under high shear mixing: 0.36 parts by weight of myristic acid, 1.78 parts by weight of isocetyl stearate, 4.96 parts by weight of pre-dispersed alumina, 2.51 parts by weight of Ebecryl 220, and 63.42 parts by weight of methyl ethyl ketone.
- the pre-dispersed alumina used in this Example was the same as the pre-dispersed alumina of Example 8.
- the magnetic dispersion was then gravure coated onto both sides of a 76.2 ⁇ m (3 mil), pre-primed polyester substrate at a 121 x 10 ⁇ 6 cms (48 microinch) caliper.
- the coated substrate was then passed through a randomizer, dried in an oven at 71°C (160°F), calendered, and cured with 10 Mrads of electron beam radiation (200 keV) in an inert atmosphere comprising no more than 75 ppm O2.
- the resulting magnetic recording medium showed a squareness of 0.45, a 60°C gloss of 135, a remanence of 700 Gauss and would be particularly suitable for forming magnetic recording diskettes.
- Disperbyk 161 (amine functional polymeric dispersant available from BYK-Chemie U.S.A.) at 30% solids in methyl ethyl ketone, 3.30 parts by weight carbon black, and enough methyl ethyl ketone to dilute the mixture to 40% solids were sequentially added to the mixture.
- the mixture was then mixed in the high shear mechanical mixer for an additional 30 minutes and then milled pass to pass in the horizontal sand mill until smooth.
- the magnetic dispersion was then gravure coated onto both sides of a 76.2 ⁇ m (3 mil), pre-primed polyester substrate at a 254 x 10 ⁇ 6 cms (100 microinch) caliper.
- the coated substrate was then dried in an oven at 71°C (160°F), calendered, and cured with 10 Mrads of electron beam radiation (200 keV) in an inert atmosphere comprising no more than 75 ppm O2.
- the resulting magnetic recording medium would be particularly suitable for forming magnetic recording diskettes.
- pre-dispersed alumina was added to the mixture. After this, the mixture was mixed for 1/2 hour with the high shear mixer and then milled pass to pass in the horizontal sand mill until smooth.
- the pre-dispersed alumina used in this Example was the same as the pre-dispersed alumina of Example 5.
- the following ingredients were added to the magnetic dispersion in order under high shear mixing as follows: 0.097 parts by weight of myristic acid, 0.84 parts by weight of isocetyl stearate, 1.58 parts by weight of Ebecryl 220, and 22.57 parts by weight of methyl ethyl ketone.
- the magnetic dispersion was then knife coated onto a 76.2 ⁇ m (3 mil), pre-primed polyester substrate at a 254 x 10 ⁇ 6 cms (100 microinch) caliper.
- the coated substrate was then dried in an oven at 71°C (160°F), calendered, and cured with 10 Mrads of electron beam radiation (200 keV) in an inert atmosphere comprising no more than 75 ppm O2.
- the resulting magnetic recording medium would be particularly suitable for forming magnetic recording diskettes.
- Coating the dispersions onto a pre-primed substrate The backside dispersion was coated onto one side of a thin gauge, pre-primed polyester substrate. The coated substrate was then dried at 60°C (140°F). Next, the magnetic dispersion was coated onto the other side of the pre-primed polyester substrate. The coated substrate was then passed through a magnetic field (4700 to 5400 Gauss) to orient the magnetic pigment. After this, the coated substrate was again dried at 60°C (140°F) and then the magnetic coating and the backside coating were calendered. The backside coating and the magnetic coating were then cured with 8 megarads of electron beam radiation in a N2 atmosphere containing no more than 50 ppm O2.
- the resulting magnetic recording medium showed a squareness of 0.803, a coercivity of 1497 Oe, and a remanence of 2650 gauss. All electromagnetic measurements were made with a vibrating sample magnetometer ("VSM”) at 12.5 kOe.
- VSM vibrating sample magnetometer
- a magnetic recording medium was prepared as described in Example 12, except that the magnetic dispersion was prepared as follows: 333 grams of a 75% by weight solution of Dispersant II in toluene, 50 grams of a 50% by weight solution of Dispersant I in methyl ethyl ketone, 2.5 lbs (1.1 kg) of a 35% by weight solution of a radiation curable polymer (prepared in accordance with Sample 2 of Example 1) in methyl ethyl ketone, and then 4.3 lbs (1.95 kg) of a 15% by weight solution of Estane 5703 in a solvent (85% by weight methyl ethyl ketone, 15% by weight toluene) were sequentially added to 3.81 lbs (1.73 kg) of methyl ethyl ketone. The resulting mixture was mixed in a high shear mixer for 10 minutes. The mixing apparatus was then purged with N2 gas.
- the resulting magnetic recording medium showed a squareness of 0.788, a coercivity of 1507 Oe, and a remanence of 2481 gauss. All measurements were made using a VSM at 12.5 kOe.
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- Paints Or Removers (AREA)
- Magnetic Record Carriers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacturing Of Magnetic Record Carriers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
- The present invention relates to novel, monomeric, oligomeric or polymeric dispersants comprising at least one dispersing moiety and at least one specified radiation curable moiety.
-
- Dispersants of the present invention may be prepared from an α-methylstyrene functionalized, isocyanate of the formula
wherein this formula represents
hereinafter referred to as "meta TMI", or
hereinafter referred to as "para TMI". Preferably, the α-methylstyrene functionalized isocyanate is meta TMI. Hereinafter, the term "TMI" without either the meta or para suffix shall mean both meta and para TMI, collectively. TMI has been described in Dexter et al., "M-TMI, A Novel Unsaturated Aliphatic Isocyanate", Journal of Coatings Technology, Vol. 58, No. 737, pp. 43-47 (June 1986); U.S. Pat. No. 4,853,478; U.S. Pat. No. 4,839,230; U.S. PAT. No. 4,788,303; and U.S. Pat. No. 4,617,349. - The subject invention provides a novel class of dispersants comprising monomeric, oligomeric, or polymeric dispersants comprising at least one dispersing moiety and at least one radiation curable moiety of the formula
wherein this formula represents
Such dispersants shall be referred to hereinafter as "α-methylstyrene functionalized" dispersants. Examples of suitable dispersing moieties include -SO₃M, wherein M is Na⁺, K⁺, Li⁺, NH₄⁺, and the like; quaternary ammonium moieties;
and the like. Advantageously the novel α-methylstyrene functionalized dispersants are capable of crosslinking with the other radiation curable binder materials of the type described in the parent application to this divisional application, when exposed to ionizing radiation in the presence of the free radical generator. -
- In this formula, m is an integer from 1 to 5. Phosphorylated polyoxyalkyl polyols are described in U.S. Pat. No. 4,889,895. All or only a portion of the hydroxy groups of the phosphorylated polyoxyalkyl polyol may be reacted with NCO groups of the TMI. Preferably, the TMI is reacted with the polyol in an amount such that the ratio of NCO groups to OH groups is about 0.6.
- Another preferred difunctional dispersant may be prepared by reacting TMI with a polyoxyalkylated quaternary ammonium polyol such as the Emcol brand dispersing agents commercially available from Witco Chemical, New York, New York. The Emcol materials are exemplified by the formula
In the above formula, ⁻X typically is phosphate, acetate, or chloride. All or only a portion of the hydroxy groups of such polyols may be reacted with the NCO groups of the TMI. It is noted that the Emcol materials typically contain other free polyols. Preferably, therefore, the TMI is reacted with such polyols in an amount such that the ratio of NCO groups to OH groups of the polyoxyalkylated quaternary ammonium polyol is about 2.2:1. In this way, all of the hydroxy groups of the other polyols and the polyoxyalkylated quaternary ammonium polyol are reacted with TMI. - The dispersants of the subject invention can be used in the field of magnetic recording media.
- Magnetic recording media generally comprise a magnetizable layer coated on at least one side of a nonmagnetizable substrate. For particulate magnetic recording media, the magnetizable layer comprises a magnetic pigment dispersed in a polymeric binder. In addition to dispersants the magnetizable layer may also include other components such as lubricants; abrasives; thermal stabilizers; antioxidants; wetting agents,; antistatic agents; fungicides; bacteriocides; surfactants; coating aids; nonmagnetic pigments; and the like.
- Some forms of magnetic recording media, such as flexible magnetic recording tape, also have a backside coating applied to the other side of the nonmagnetizable substrate in order to improve the durability,conductivity, and tracking characteristics of the media. The backside coating typically comprises a polymeric binder, but may also include other components such as dispersants; lubricants; abrasives; thermal stabilisers; antioxidants; wetting agents; antistatic agents; fungicides; bacteriocides; surfactants; coating aids; nonmagnetic pigments; and the like.
- As mentioned, the components of the magnetizable layer preferably include at least one dispersant to facilitate the dispersion of the magnetic pigment in the polymeric binder.
- In the case of higher surface area pigments, e.g. pigments having a surface area of 25 m²/g to 70 m²/g such as cobalt-doped Fe₂O₃, barium ferrite, and metal particle pigments, a preferred class of dispersants comprises novel monomeric, oligomeric, or polymeric dispersants of the present invention.
- The present invention will now be further described with regard to the following examples. The term "RE" where it appears in the following text means either Reference Example or Reference Examples, as the context requires.
- Radiation curable polymer samples of the present invention were prepared under ambient conditions by reacting a hydroxy functional polymer (PKHH UCAR phenoxy resin commercially available from Union Carbide Corporation) with meta-TMI in the following amounts:
Sample Parts by weight of Hydroxy Functional Polymer Parts by weight of meta-TMI % OH groups reacted with meta-TMI 1 100.0 14.16 20 2 100.0 35.40 50 3 100.0 42.46 60 4 100.0 56.62 80 - For each sample, the hydroxy-functional polymer was first dissolved in 233 parts by weight methyl ethyl ketone. Next, 200 ppm (based on total weight of the hydroxy functional polymer and the meta-TMI) of BHT gellation inhibitor and 0.15 weight percent (based on the total weight of the hydroxy functional polymer and the meta-TMI) of dibutyltindilaurate catalyst were added to the solution with mixing. The meta-TMI was then slowly added with mixing. After all of the meta-TMI had been added, the reaction between the hydroxy-functional polymer and the meta-TMI was monitored by measuring the IR absorption peak of the NCO group (2250 cm⁻¹) from the meta-TMI. The reaction was deemed to be complete when an IR absorption peak for the NCO group could no longer be detected.
- Based upon a 15,000 gram batch, a maximum exotherm occurred about 1 hour after the meta-TMI had been added to the reaction mixture. After the maximum exotherm temperature was reached, the reaction mixture was heated to maintain the reaction mixture at 49°C (120°F).
- After the reaction is complete, the reaction mixture was cooled to room temperature. Optionally at this time, additional methyl ethyl ketone may be added to the reaction mixture in order to reduce the weight percent solids to about 33% solids. Adding additional solvent in this manner lowers the viscosity of the reaction mixture, thereby facilitating subsequent processing.
- The Tg of Samples 1, 2, 3, and 4 were 80°C, 72°C, 68°C and 65°C, respectively, as measured using the DSC technique.
- A magnetic dispersion of the present invention was prepared from the following ingredients:
Ingredient Parts by Weight γ-Fe₂O₃ 100.00 Carbon black 5.00 Al₂O₃ 7.00 Phosphate acid ester acrylate commercially available as L-51 from Lord Corporation (50% by weight in tetrahydrofuran) 10.00 Emcol Phosphate 2.00 Radiation curable polymer (Sample 3 from Example 1) (32% by weight in methyl ethyl ketone) 67.50 Methyl ethyl ketone 135.48 - One 50.4 gram aliquot of the dispersion was blended with 1.11 grams of PETA. The resulting mixture was then coated onto a 3 mil, pre-primed polyester film, dried, and cured with 10 Mrads of electron beam radiation (200 keV) in an inert atmosphere containing less than 75 ppm O₂.
- The resulting magnetic recording medium was tested for crosslink density using the "MEK double rub" test. According to this test, the sample was rubbed vigorously with back and forth rubs using a paper towel that had been soaked in methyl ethyl ketone. Failure occurred when the rubbing action broke through the magnetic coating to the polyester film. The magnetic coating of this sample was not broken through to the polyester film until after 30 back and forth rubs.
- A magnetic recording medium was prepared using the procedure of RE 2 except that hydantoin hexacrylate was used in place of PETA. The resulting magnetic recording medium passed the MEK double rub test without showing any break through to the polyester film until after 10 back and forth rubs.
- A magnetic recording medium was prepared using the procedure of RE 2 except that tris(2-hydroxyethyl) triacrylate (available as Sartomer 368 from Sartomer Co.) was used in place of PETA. The resulting magnetic recording medium passed the MEK double rub test without showing any break through to the polyester film until after 20 back and forth rubs.
- In a first step, 100.00 parts by weight gamma-Fe₂O₃, 9.00 parts by weight of carbon black, 24.14 parts by weight of Disperbyk-160 (29% by weight solution of a polyurethane polymer having pendant tertiary amine wetting groups commercially available from BYK-Chemie USA), 18.09 parts by weight of a 33% by weight solution of a radiation curable polymer (prepared in accordance with Sample 4 from Example 1) in methyl ethyl ketone, 59.73 parts by weight of a 15% by weight solution of a polyurethane polymer (Estane 5703 commercially available from The B. F. Goodrich Company) in a solvent (85% by weight methyl ethyl ketone, 15% by weight toluene), 0.07 parts by weight of propyl gallate stabilizer, 0.07 parts by weight of another stabilizer (commercially available as Irgafos 168 from CIBA-GEIGY Corp.), and 93.4 parts by weight of methyl ethyl ketone were combined and milled until smooth to form a homogeneous solution.
- Next, 12.4 parts by weight of pre-dispersed alumina, 9.85 parts by weight of an aromatic urethane hexacrylate oligomer (Ebycryl 220 commercially available from Radcure Specialties, Inc.), 1.00 parts by weight myristic acid, 4.00 parts by weight isocetyl stearate, 0.23 parts by weight diiodomethyl-paratolylsulfone (available as Amical-48 from Angus Chemical Co.), and 134.2 parts by weight methyl ethyl ketone were sequentially blended into the dispersion in the order listed. As used in this example, "pre-dispersed" alumina means that 100 parts by weight of alumina had previously been dispersed in 40.1 parts by weight of methyl ethyl ketone, 18.2 parts by weight of a radiation curable polymer (prepared in accordance with Sample 2 from Example 1), 20.7 parts by weight of Disperbyk-160, 0.07 parts by weight of propyl gallate, and 0.07 parts by weight of Irgafos 168.
- The resulting blend was then gravure coated onto both sides of a 3-mil, pre-primed polyester substrate at a 228 x 10⁻⁶ cms (90 microinch) caliper. The coated substrate was then passed through a randomizer, dried in an oven at 71°C (160°F) calendered, and cured with 10 Mrads of electron beam radiation (200 keV) in an inert atmosphere comprising no more than 75 ppm O₂. The resulting magnetic recording medium showed a 60° gloss of 120 and a squareness of 0.50. The resulting media would be particularly suitable for forming magnetic recording diskettes.
- 100.0 parts by weight of Emcol Phosphate quaternary ammonium polyol (0.0909 equivalents of OH) 0.03 parts by weight of BHT, and 0.28 parts by weight dibutyltindilaurate were dissolved in 140.5 parts by weight of methyl ethyl ketone. Next 40.2 parts by weight of meta-TMI (0.2000 equivalents of NCO) was slowly added at room temperature. The resulting reaction mixture was stirred for 30 minutes. After 30 minutes, stirring was stopped, and the reaction was allowed to proceed. The reaction was complete after 1 day when an IR absorption for NCO at 2250 cm⁻¹ could no longer be detected. Three hours after the meta-TMI had been added, a 1500 gram batch showed a maximum exotherm of 36°C. The resulting α-methylstyrene functionalized dispersant shall be referred to hereinafter as "Dispersant I".
- 133.33 parts by weight of a 75% solution of a phosphorylated polyoxyalkyl diol (0.238 equivalents OH) in toluene, 0.03 parts by weight BHT, and 0.28 parts by weight dibutyltindilaurate were dissolved in 38.37 parts by weight toluene. Next, 28.70 parts by weight meta-TMI (0.143 equivalents NCO) was slowly added at room temperature. The resulting reaction mixture was stirred for 30 minutes. After 30 minutes, stirring was stopped, and the reaction was allowed to proceed. The reaction was complete after 2 days when an IR absorption for NCO at 2250 cm⁻¹ could no longer be detected. Six hours after the meta-TMI had been added, a 10,000 gram batch showed a maximum exotherm of 37°C. The resulting α-methylstyrene functionalized dispersant shall be referred to hereinafter as "Dispersant II".
- 0.075 parts by weight of Irgafos 168 stabilizer (CIBA-GEIGY Corp.), 0.075 parts by weight of propyl gallate, 6.39 parts by weight of a 76.7% by weight solution of Dispersant II in toluene, and then 1.10 parts by weight of a 50% by weight solution of Dispersant I in methyl ethyl ketone were sequentially added into 73.35 parts by weight of methyl ethyl ketone. The resulting mixture was then mixed in a high shear mechanical mixer for 10 minutes.
- Next, 100.00 parts by weight of Co-γ-Fe₂O₃ magnetic pigment having a surface area of 40 m²/g was slowly added to the mixture. After adding the pigment, the mixture was mixed in a high shear mechanical mixer for an additional 1.5 hours.
- Next, 13.20 parts by weight of pre-dispersed alumina, 16.31 parts by weight of a 34.7% by weight solution of a radiation curable polymer (prepared in accordance with Sample 4 of Example 1) in methyl ethyl ketone, and then 70.13 parts by weight of a 15% by weight solution of Estane 5703 in a solvent (85% by weight methyl ethyl ketone, 15% by weight toluene) were slowly added sequentially into the mixture. The mixture was then mixed for an additional 1.5 hrs in the high shear mechanical mixer. After this, the mixture was milled pass to pass until smooth in a horizontal sand mill using ceramic media.
- As used in this Example 8, "pre-dispersed" alumina means that 100 parts by weight of alumina had previously been dispersed in 1 part by weight Emcol Phosphate, 1.3 parts by weight of a 75% by weight solution of phosphorylated polyoxyalkyl polyol in toluene, 30.6 parts by weight methyl ethyl ketone, and 3.4 parts by weight of cyclohexanone.
- Next, 6.50 parts by weight of carbon black, 5.00 parts by weight of a 40% by weight solution of BYK LP-M 5960 (amine-functional polymeric dispersant available from BYK-Chemie GmbH) in cyclohexanone and then 6.60 parts by weight of methyl ethyl ketone were sequentially blended into the mixture. The mixture was then mixed in the high shear mechanical mixer for 1.5 hrs. After mixing, the mixture was milled pass to pass until smooth in the horizontal sand mill.
- Just prior to coating the resulting magnetic recording dispersion onto a substrate, to 100 parts by weight of the magnetic dispersion, the following ingredients were added in order under high shear mixing: 0.33 parts by weight of myristic acid, 1.67 parts by weight of isocetyl stearate, 3.38 parts by weight of Ebecryl 220, and 69.2 parts by weight of methyl ethyl ketone.
- The resulting blend was then gravure coated onto both sides of a 76.2 µm (3 mil), pre-primed polyester substrate at a 114 x 10-6 cms (45 microinch) caliper. The coated substrate was then passed through a randomizer, dried in an oven at 71°C (160°F) calendered, and cured with 10 Mrads of electron beam radiation (200 keV) in an inert atmosphere comprising no more than 75 ppm O₂. The resulting magnetic recording medium showed a squareness of 0.7, a 60° gloss of 130, and a remanence, BR, of 800 gauss. The resulting magnetic recording medium would be particularly suitable for forming magnetic recording diskettes.
- 0.033 parts by weight of tetramethylthiuram disulfide, 0.033 parts by weight propyl gallate, 3.48 parts by weight of a 75% by weight solution of Dispersant II in toluene, and then 0.66 parts by weight of a 50% by weight solution of Dispersant I in methyl ethyl ketone were sequentially added to 28.7 parts by weight of methyl ethyl ketone. The resulting mixture was then mixed in a high shear mechanical mixer for 10 minutes.
- Next, 43.50 parts by weight of Co-γ-Fe₂O₃ magnetic pigment having a surface area of 40 m²/g was slowly added to the mixture. After adding the pigment, the mixture was mixed in a high shear mechanical mixer for an additional 1.5 hours.
- Next, 11.80 parts by weight of a 36.0% by weight solution of a radiation curable polymer (prepared in accordance with Sample 2 of Example 1) in methyl ethyl ketone and then 18.93 parts by weight of a 15% by weight solution of Estane 5703 in methyl ethyl ketone were slowly added sequentially into the mixture. The mixture was then mixed in a high shear mechanical mixer for an additional 1.5 hr. The mixture was then milled pass to pass until smooth in a horizontal sand mill using ceramic media.
- Next, 3.04 parts by weight of carbon black, 2.18 parts by weight of a 40.0% by weight solution of BYK LP-M 5960 (amine functional polymeric dispersant available from BYK-Chemie GmbH) in cyclohexanone, and then 9.94 parts by weight of methyl ethyl ketone were sequentially added to the mixture. The mixture was then mixed in the high shear mechanical mixer for 1/2 hr. After this, the mixture was milled in the horizontal sand mill pass to pass until smooth.
- Just prior to coating the resulting magnetic dispersion onto a substrate, to 100 parts by weight of the magnetic dispersion, the following ingredients were added in order under high shear mixing: 0.36 parts by weight of myristic acid, 1.78 parts by weight of isocetyl stearate, 4.96 parts by weight of pre-dispersed alumina, 2.51 parts by weight of Ebecryl 220, and 63.42 parts by weight of methyl ethyl ketone. The pre-dispersed alumina used in this Example was the same as the pre-dispersed alumina of Example 8.
- The magnetic dispersion was then gravure coated onto both sides of a 76.2 µm (3 mil), pre-primed polyester substrate at a 121 x 10⁻⁶ cms (48 microinch) caliper. The coated substrate was then passed through a randomizer, dried in an oven at 71°C (160°F), calendered, and cured with 10 Mrads of electron beam radiation (200 keV) in an inert atmosphere comprising no more than 75 ppm O₂. The resulting magnetic recording medium showed a squareness of 0.45, a 60°C gloss of 135, a remanence of 700 Gauss and would be particularly suitable for forming magnetic recording diskettes.
- 100.00 parts by weight of barium ferrite magnetic pigment, 6.70 parts by weight of alumina, 6.7 parts by weight Dispersant II at 75% solids in toluene, 1.5 parts by weight Dispersant I at 50% solids in methyl ethyl ketone, 8.7 parts by weight of a radiation curable polymer (prepared in accordance with Sample 2 of Example 1) at 35% solids in methyl ethyl ketone, and then 20.3 parts by weight of Estane 5703 at 15% solids in a solvent (85% by weight methyl ethyl ketone, 15% by weight toluene) were added to 138 parts by weight of methyl ethyl ketone. The mixture was mixed in a high shear mechanical mixer for 1 hour and then milled pass to pass until smooth in a horizontal sand mill using ceramic media.
- Next, 5.0 parts by weight Disperbyk 161 (amine functional polymeric dispersant available from BYK-Chemie U.S.A.) at 30% solids in methyl ethyl ketone, 3.30 parts by weight carbon black, and enough methyl ethyl ketone to dilute the mixture to 40% solids were sequentially added to the mixture. The mixture was then mixed in the high shear mechanical mixer for an additional 30 minutes and then milled pass to pass in the horizontal sand mill until smooth.
- Just prior to coating the resulting magnetic dispersion onto a substrate, 2.60 parts by weight lubricant, 2.76 parts by weight Ebecryl 220, and enough methyl ethyl ketone to dilute the dispersion to 35% solids were sequentially blended into the dispersion using high shear mixing.
- The magnetic dispersion was then gravure coated onto both sides of a 76.2 µm (3 mil), pre-primed polyester substrate at a 254 x 10⁻⁶ cms (100 microinch) caliper. The coated substrate was then dried in an oven at 71°C (160°F), calendered, and cured with 10 Mrads of electron beam radiation (200 keV) in an inert atmosphere comprising no more than 75 ppm O₂. The resulting magnetic recording medium would be particularly suitable for forming magnetic recording diskettes.
- 0.015 parts by weight of Irgafos 168, 0.015 parts by weight of propyl gallate, and then 0.83 parts by weight of a 75% by weight solution of Dispersant II in toluene were sequentially added to 19.88 parts by weight of methyl ethyl ketone. The resulting mixture was mixed with a high shear mechanical mixer for 10 minutes.
- Next, 20.0 parts by weight of barium ferrite magnetic pigment wore slowly added to the mixture. After this, the mixture was mixed in the high shear mixer for an additional 1.5 hours.
- Next, 3.01 parts by weight of a 35.1% by weight solution of a radiation curable polymer (prepared in accordance with Sample 4 of Example 1) and then 2.50 parts by weight of a 30% by weight solution of Toyobo UR8300 (a sulfonated polyurethane polymer available from Toyobo Co., Ltd.) were slowly added sequentially to the mixture. The mixture was then mixed in the high shear mixer for 1.5 hours and then milled pass to pass until smooth in a horizontal sand mill using ceramic media.
- Next, 3.60 parts by weight of carbon black and then 7.18 parts by weight of methyl ethyl ketone were sequentially added to the mixture. The mixture was then mixed in the high shear mixer for 1/2 hour and then milled pass to pass in the horizontal sand mill until smooth.
- Next, 2.28 parts by weight of pre-dispersed alumina was added to the mixture. After this, the mixture was mixed for 1/2 hour with the high shear mixer and then milled pass to pass in the horizontal sand mill until smooth. The pre-dispersed alumina used in this Example was the same as the pre-dispersed alumina of Example 5.
- Just prior to coating, to 100 parts by weight of the resulting magnetic dispersion, the following ingredients were added to the magnetic dispersion in order under high shear mixing as follows: 0.097 parts by weight of myristic acid, 0.84 parts by weight of isocetyl stearate, 1.58 parts by weight of Ebecryl 220, and 22.57 parts by weight of methyl ethyl ketone.
- The magnetic dispersion was then knife coated onto a 76.2 µm (3 mil), pre-primed polyester substrate at a 254 x 10⁻⁶ cms (100 microinch) caliper. The coated substrate was then dried in an oven at 71°C (160°F), calendered, and cured with 10 Mrads of electron beam radiation (200 keV) in an inert atmosphere comprising no more than 75 ppm O₂. The resulting magnetic recording medium would be particularly suitable for forming magnetic recording diskettes.
- a. Preparation of Backside Dispersion:
1.2 lbs (0.54 kg) of a 75% by weight solution of Dispersant II in toluene, 11.7 lbs (5.31 kg) of a 35% by weight solution of a radiation curable polymer (prepared in accordance with Sample 3 of Example 1) in methyl ethyl ketone, and then 18.2 lbs (8.25 kg) of a 15% by weight solution of Estane 5703 in a solvent (85% by weight methyl ethyl ketone, 15% by weight toluene) in methyl ethyl ketone were sequentially added to 12.9 lbs (5.85 kg) of methyl ethyl ketone. The resulting mixture was mixed with an enclosed high shear mechanical mixer for 10 minutes. - Next, 4.95 lbs (2.24 kg) of carbon black was slowly added to the mixture. After this, the mixture was mixed in the high shear mechanical mixer for 1 hour.
- Next, 11.0 lbs (4.99 kg) of TiO₂ was slowly added to the mixture. After this, the mixture was mixed with the high shear mechanical mixer for 1 hour. The mixture was then milled pass to pass until smooth in a sandmill.
- Just prior to coating the resulting backside dispersion onto a substrate, 2.92 lbs (1.32 kg) of Ebecryl 220 and 0.13 lbs (60 grams) of myristic acid were blended into the dispersion. The dispersion was also diluted to 20% solids with methyl ethyl ketone and cyclohexanone, wherein the cyclohexanone was used in an amount such that the total amount of solvent in the dispersion was comprised of 18% by weight of cyclohexanone.
- b. Preparation of magnetic dispersion:
4 grams of propyl gallate, 4 grams of Irgafos 168, 333 grams of a 75% by weight solution of Dispersant II in toluene, 25 grams of Emcol Phosphate, 2.5 lbs (1.1 kg) of a 35% by weight solution of a radiation curable polymer (prepared in accordance with Sample 2 of Example 1) in methyl ethyl ketone, and then 4.3 lbs (1.9 kg) of a 15% by weight solution of Estane 5703 in a solvent (85% by weight methyl ethyl ketone, 15% by weight toluene) were sequentially added to 3.86 lbs (1.75 kg) of methyl ethyl ketone. The resulting mixture was mixed in an enclosed high shear mixer for 10 minutes. The mixing apparatus was then purged with N₂ gas. - Next, 11.0 lbs (4.99 kg) of Fe metal particle magnetic pigment and then 0.85 lbs (0.38 kg) of alumina were slowly added sequentially to the mixture. The mixture was then mixed under the N₂ atmosphere in the high shear mixer for an additional 2 hours.
- Next, 11.7 lbs (5.31 kg) of methyl ethyl ketone was added to the mixture. The mixture was then mixed with the high shear mixer for an additional 1 hour. After this, the mixture was milled pass to pass in a sandmill until smooth using ceramic media.
- Just prior to coating the resulting magnetic dispersion onto a substrate, 0.748 lbs (0.339 kg) Ebecryl 220, 0.24 lbs (0.11 kg) of myristic acid, and 0.12 lbs (0.054 kg) of butyl stearate were blended into the dispersion. The dispersion was also diluted to 32% solids with methyl ethyl ketone and cyclohexanone, wherein the cyclohexanone was used in an amount such that the total amount of solvent in the dispersion was comprised of 18% by weight cyclohexanone.
- c. Coating the dispersions onto a pre-primed substrate:
The backside dispersion was coated onto one side of a thin gauge, pre-primed polyester substrate. The coated substrate was then dried at 60°C (140°F). Next, the magnetic dispersion was coated onto the other side of the pre-primed polyester substrate. The coated substrate was then passed through a magnetic field (4700 to 5400 Gauss) to orient the magnetic pigment. After this, the coated substrate was again dried at 60°C (140°F) and then the magnetic coating and the backside coating were calendered. The backside coating and the magnetic coating were then cured with 8 megarads of electron beam radiation in a N₂ atmosphere containing no more than 50 ppm O₂. - The resulting magnetic recording medium showed a squareness of 0.803, a coercivity of 1497 Oe, and a remanence of 2650 gauss. All electromagnetic measurements were made with a vibrating sample magnetometer ("VSM") at 12.5 kOe.
- A magnetic recording medium was prepared as described in Example 12, except that the magnetic dispersion was prepared as follows:
333 grams of a 75% by weight solution of Dispersant II in toluene, 50 grams of a 50% by weight solution of Dispersant I in methyl ethyl ketone, 2.5 lbs (1.1 kg) of a 35% by weight solution of a radiation curable polymer (prepared in accordance with Sample 2 of Example 1) in methyl ethyl ketone, and then 4.3 lbs (1.95 kg) of a 15% by weight solution of Estane 5703 in a solvent (85% by weight methyl ethyl ketone, 15% by weight toluene) were sequentially added to 3.81 lbs (1.73 kg) of methyl ethyl ketone. The resulting mixture was mixed in a high shear mixer for 10 minutes. The mixing apparatus was then purged with N₂ gas. - Next, 11.0 lbs (4.99 kg) of Fe metal particle magnetic pigment and then 0.85 lbs (.38 kg) of alumina were slowly added sequentially to the mixture. After this, the mixture was then mixed under the N₂ atmosphere for an additional 2 hours.
- Next, 11.7 lbs (5.31 kg) of methyl ethyl ketone was added to the mixture, and the mixture was then mixed for an additional 1 hour. After this, the mixture was milled pass to pass in a sandmill with ceramic media until smooth.
- Just prior to coating the resulting magnetic dispersion onto a substrate, 0.75 lbs of Ebecryl 220, 0.24 lbs (0.11 kg) of myristic acid, and then 0.12 lbs (0.054 kg) of butyl stearate were blended into the dispersion. The dispersion was also diluted to 32% solids with methyl ethyl ketone and cyclohexanone, wherein the cyclohexanone was used in an amount such that the total solvent in the dispersion wan comprised of 18% by weight cyclohexanone.
- The resulting magnetic recording medium showed a squareness of 0.788, a coercivity of 1507 Oe, and a remanence of 2481 gauss. All measurements were made using a VSM at 12.5 kOe.
- Other embodiments of this invention will be apparent to those skilled in the art from a consideration of this specification or from practice of the invention disclosed herein. Various omissions, modifications, and changes to the principles described herein may be made by one skilled in the art without departing from the true scope and spirit of the invention which is indicated by the following claims.
Claims (4)
- The dispersant of any preceding claim, wherein the dispersant is obtained by reacting an α-methylstyrene functionalized isocyanate with a phosphorylated polyoxyalkylated polyol.
- The dispersant of any one of preceding claims 1-2, wherein the dispersant is obtained by reacting an α-methylstyrene functionalized isocyanate with a polyoxyalkylated quaternary ammonium polyol.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US775145 | 1991-10-09 | ||
US07/775,145 US5380905A (en) | 1991-10-09 | 1991-10-09 | Magnetic recording medium having radiation curable binder with α-methylstyrene unsaturation |
EP92308998A EP0536956B1 (en) | 1991-10-09 | 1992-10-01 | Magnetic recording medium |
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EP92308998A Division EP0536956B1 (en) | 1991-10-09 | 1992-10-01 | Magnetic recording medium |
EP92308998.1 Division | 1992-10-01 |
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EP0709831A2 true EP0709831A2 (en) | 1996-05-01 |
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EP92308998A Expired - Lifetime EP0536956B1 (en) | 1991-10-09 | 1992-10-01 | Magnetic recording medium |
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EP92308998A Expired - Lifetime EP0536956B1 (en) | 1991-10-09 | 1992-10-01 | Magnetic recording medium |
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EP (2) | EP0709831B1 (en) |
JP (2) | JP3357401B2 (en) |
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CN (1) | CN1071520A (en) |
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US6265060B1 (en) * | 1995-03-15 | 2001-07-24 | Imation Corp. | Magnetic recording medium incorporating fluorine-containing, solvent-soluble vinyl copolymer having no vinyl chloride or vinylidene chloride components |
AU2327300A (en) | 1999-02-10 | 2000-08-29 | Hitachi Maxell, Ltd. | Magnetic recording medium, and magnetic powder and method for preparing the same |
US6541109B1 (en) | 1999-10-08 | 2003-04-01 | 3M Innovative Properties Company | Release coating formulation providing low adhesion release surfaces for pressure sensitive adhesives |
US6610426B2 (en) * | 2000-10-12 | 2003-08-26 | Fuji Photo Film Co., Ltd. | Magnetic recording medium containing a binder of trifunctional or higher aliphatic (meth) acrylate compound |
JP3886968B2 (en) * | 2002-03-18 | 2007-02-28 | 日立マクセル株式会社 | Magnetic recording medium and magnetic recording cartridge |
US7494728B2 (en) * | 2002-04-25 | 2009-02-24 | Hitachi Maxell, Ltd. | Magnetic tape and magnetic tape cartridge |
US6964811B2 (en) * | 2002-09-20 | 2005-11-15 | Hitachi Maxell, Ltd. | Magnetic powder, method for producing the same and magnetic recording medium comprising the same |
US7238439B2 (en) * | 2003-02-19 | 2007-07-03 | Hitachi Maxell, Ltd. | Magnetic recording medium containing particles with a core containing a Fe16N2 phase |
US7135122B2 (en) * | 2004-03-31 | 2006-11-14 | Freudenberg-Nok General Partnership | Polytetrafluoroethylene composites |
US7452577B2 (en) * | 2004-06-30 | 2008-11-18 | Freudenberg-Nok General Partnership | Electron beam curing of fabricated polymeric structures |
US7342072B2 (en) | 2004-06-30 | 2008-03-11 | Freudenberg-Nok General Partnership | Bimodal compounds having an elastomeric moiety |
US20060000801A1 (en) * | 2004-06-30 | 2006-01-05 | Park Edward H | Surface bonding in halogenated polymeric components |
US7244329B2 (en) * | 2004-06-30 | 2007-07-17 | Freudenberg-Nok General Partnership | Electron beam curing in a composite having a flow resistant adhesive layer |
US7521508B2 (en) * | 2004-06-30 | 2009-04-21 | Freudenberg-Nok General Partnership | Electron beam inter-curing of plastic and elastomer blends |
US7230038B2 (en) * | 2004-06-30 | 2007-06-12 | Freudenberg-Nok General Partnership | Branched chain fluoropolymers |
US7381765B2 (en) | 2004-11-08 | 2008-06-03 | Freudenberg-Nok General Partnership | Electrostatically dissipative fluoropolymers |
US20060100368A1 (en) * | 2004-11-08 | 2006-05-11 | Park Edward H | Elastomer gum polymer systems |
US20060099368A1 (en) * | 2004-11-08 | 2006-05-11 | Park Edward H | Fuel hose with a fluoropolymer inner layer |
US20070045967A1 (en) * | 2005-08-31 | 2007-03-01 | Freudenberg-Nok General Partnership | Assemblies sealed with multilayer composite torsion seals having a layer of dispersed fluoroelastomer in thermoplastic |
US20070044906A1 (en) * | 2005-08-31 | 2007-03-01 | Freudenberg-Nok General Partnership | Multilayer polymeric composites having a layer of dispersed fluoroelastomer in thermoplastic |
US20070048476A1 (en) * | 2005-08-31 | 2007-03-01 | Freudenberg-Nok General Partnership | Assemblies sealed with multilayer composite compression seals having a layer of dispersed fluoroelastomer in thermoplastic |
US7863365B2 (en) | 2006-12-20 | 2011-01-04 | Freudenberg-Nok General Partnership | Robust magnetizable elastomeric thermoplastic blends |
JP5104053B2 (en) * | 2007-06-15 | 2012-12-19 | 東洋インキScホールディングス株式会社 | Method for producing coating composition |
CN103160147A (en) * | 2011-12-14 | 2013-06-19 | 吴江市冰心文教用品有限公司 | Magnetic pigment |
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- 1992-10-01 EP EP95119618A patent/EP0709831B1/en not_active Expired - Lifetime
- 1992-10-01 EP EP92308998A patent/EP0536956B1/en not_active Expired - Lifetime
- 1992-10-01 DE DE69227928T patent/DE69227928T2/en not_active Expired - Fee Related
- 1992-10-08 KR KR1019920018534A patent/KR930008726A/en active IP Right Grant
- 1992-10-08 JP JP26988792A patent/JP3357401B2/en not_active Expired - Fee Related
- 1992-10-09 CN CN92111427A patent/CN1071520A/en active Pending
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Publication number | Priority date | Publication date | Assignee | Title |
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EP0348975A2 (en) * | 1988-06-30 | 1990-01-03 | Kawasaki Steel Corporation | Copolymer of polymerizable components in naphtha oil and maleic anhydride, process for producing said copolymer, and derivatives thereof |
DE3938002A1 (en) * | 1988-11-15 | 1990-05-17 | Sakura Color Prod Corp | WATER-BASED PIGMENT INK COMPOSITIONS FOR USE IN MARKING PENCILS |
EP0422222A1 (en) * | 1989-04-17 | 1991-04-17 | Kawasaki Steel Corporation | Dispersing agent and cement admixture |
Also Published As
Publication number | Publication date |
---|---|
EP0536956B1 (en) | 1996-09-11 |
DE69227928D1 (en) | 1999-01-28 |
US5380905A (en) | 1995-01-10 |
EP0709831B1 (en) | 1998-12-16 |
JPH05217148A (en) | 1993-08-27 |
DE69213636T2 (en) | 1997-03-27 |
DE69227928T2 (en) | 1999-08-05 |
DE69213636D1 (en) | 1996-10-17 |
EP0709831A3 (en) | 1996-05-15 |
US5523115A (en) | 1996-06-04 |
JP2002155124A (en) | 2002-05-28 |
KR930008726A (en) | 1993-05-21 |
CN1071520A (en) | 1993-04-28 |
JP3357401B2 (en) | 2002-12-16 |
EP0536956A1 (en) | 1993-04-14 |
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